Abstract
X-ray diffraction with a position-sensitive detector (XRD-PSD) was used to make a time-resolved study of the dynamics of deposition and dehydration of Na-montmorillonite crystallites on flat substrates from deionized water suspensions. The static PSD geometry and simultaneous counting procedure allowed the acquisition of high-resolution data on the dynamics of interlayer and interparticle arrangements during dehydration. Three experimental datasets of Na-smectite dehydration are presented, each one representing different initial sample states (suspension, slurry and re-wetted thin film). The computer program NEWMOD was used to simulate one of the three datasets (dehydration of a smectite suspension) and thus obtain the apparent changes in relative proportions of different 00l values as smectite crystallites formed and dehydrated. Two types of diffracting domains formed: water-dispersed ‘packets’ of 1–2 smectite layers gaining long-range order in the c axis direction as water was lost to evaporation, and smectite layers deposited as hydrated crystallites with variable interlayer water contents. The experimental patterns show the rapid step-wise transition of Na-montmorillonite layers from d values of ∼55 to 18.5, 15.4 and 12.5 Å, with variations that depended upon how the hydrated smectite sample was prepared. The simulations show that there was a wide range of d values whose frequency distribution changed as dehydration proceeded and that transient d values occurred between the peaks observed experimentally. The data obtained in this study illustrate that XRD-PSD instruments have great potential in providing detailed data on the rapid kinetics of interlayer reorganization.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Batchelder, M. and Cressey, G. (1998) Rapid, accurate phase quantification of clay-bearing samples using a position-sensitive X-ray detector. Clays and Clay Minerals, 46, 183–194.
Bergaya, F. and Vayer, M. (1997) CEC of clays: measurement by adsorption of a copper ethylenediamine complex. Applied Clay Science, 12, 275–280.
Blanton, T.N., Huang T.C., Toraya, H., Hubbard, C.R., Robie, S.B., Louër, D., Göbel, H.E., Will, G., Gilles, R. and Raferty, T. (1995) JCPDS — International Centre for Diffraction Data round robin study of silver behenate. A possible low-angle X-ray diffraction calibration standard. Powder Diffraction, 10, 91–95.
Boek, E.S., Coveney, P.V. and Skipper, N.T. (1995a) Monte Carlo molecular modeling studies of hydrated Li-, Na-, and K-smectites: Understanding the role of potassium as a clay swelling inhibitor. Journal of the American Chemical Society, 117, 12608–12617.
Boek, E.S., Coveney, P.V. and Skipper, N.T. (1995b) Molecular modeling of clay hydration: A study of hysteresis loops in the swelling curves of sodium montmorillonites. Langmuir, 11, 4629–4631.
Bradley, W.F., Grim, R.E. and Clark, G.L. (1937) A study of the behaviour of montmorillonite upon wetting. Zeitschrift Kristallographie, A97, 216–222.
Brindley, G.W. (1980) Quantitative X-ray mineral analysis of clays. Pp. 411–438 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley and G. Brown, editors). Monograph 5, Mineralogical Society, London.
Cases, J., Bérend, I., Besson, G., François, M., Uriot, J.P., Thomas, F. and Poirier, J.E. (1992) Mechanism of adsorption and desorption of water vapor by homionic montmorillonite. 1. The sodium-exchanged form. Langmuir, 8, 2730–2739.
Chang, F-R.C., Skipper, N.T. and Sposito, G. (1995) Computer simulation of interlayer molecular structure in sodium montmorillonite hydrates. Langmuir, 11, 2734–2741.
Chatterjee, A., Iwasaki, T., Ebina, T. and Miyamoto, A. (1999) A DTF study on clay-cation-water interaction in montmorillonite and beidellite. Computational Materials Science, 14, 119–124.
Collins, D.R., Fitch, A.N. and Catlow, R.A. (1992) Dehydration of vermiculites and montmorillonites: A time-resolved powder neutron diffraction study. Journal of Materials Chemistry, 2, 865–873.
da Silva, G., Fossum, J., DiMasi, E., Måløy, K. and Lutnæs, S. (2002) Synchrotron X-ray scattering studies of water intercalation in a layered synthetic silicate. Physical Review E, 66, 011303-1-011303-8.
DiMasi, E., Fossum, J., Gog, T. and Venkataraman, C. (2001) Orientational order in gravity dispersed clay colloids: A synchrotron X-ray scattering study of Na fluorohectorite suspension. Physical Review E, 64, 061704-1-061704-7.
Glaeser, R. and Méring, J. (1968) Homogeneous hydration domains of the smectites. Comptes Rendus de Seances de l’academie des sciences, Paris, 267, 436–466.
Howard, S.A. and Preston, K.D. (1989) Profile fitting of powder diffraction patterns. Pp. 217–276 in: Modern Powder Diffraction (D.L. Bish and J.E. Post, editors). Reviews in Mineralogy, 20. Mineralogical Society of America, Washington, D.C.
Karaborni, S., Smit, B., Heidug, W., Urai, J. and van Oort, E. (1996) The swelling of clays: molecular simulations of the hydration of montmorillonite. Science, 271, 1102–1104.
Kawamura, K., Ichikawa, Y., Nakano, M., Kitiyama, K. and Kawamura, H. (1999) Swelling properties of smectite up to 90°C. In-situ X-ray diffraction experiments and molecular dynamic simulations. Engineering Geology, 54, 75–79.
Keren, R. and Shainberg, I. (1975) Water vapor isotherms and heat of immersion of Na/Ca montmorillonite systems — 1: homoionic clay. Clays and Clay Minerals, 23, 193–200.
MacEwan, D.M.C. and Wilson, M.J. (1980) Interlayer and intercalation complexes of clay minerals. Pp. 197–248 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley and G. Brown, editors). Monograph 5, Mineralogical Society, London.
Moore, D.M. and Hower, J. (1986) Ordered interstratification of dehydrated and hydrated smectite. Clays and Clay Minerals, 34, 379–384.
Moore, D.M. and Reynolds, R.C. (1997) X-ray Diffraction and the Identification and Analysis of Clay Minerals. Oxford University Press, Oxford, UK.
Reynolds, R.C., Jr. and Reynolds, R.C., III (1996) NEWMOD: The Calculation of One-Dimensional X-ray Diffraction Patterns of Mixed-Layered Clay Minerals. Computer Program. 8 Brook Road, Hanover, New Hampshire, USA.
Skipper, N.T., Refson, K. and McConnell, J.D.C. (1991) Computer simulation of interlayer water in 2: 1 clays. Journal of Chemical Physics, 94, 7434–7445.
Skipper, N., Chang, F.-R. and Sposito, G. (1995) Monte Carlo simulation of interlayer molecule structure in swelling clay minerals. 1. Methodology. Clays and Clay Minerals, 43, 285–293.
Sposito, G., Park, S.-H. and Sutton, R. (1999) Monte Carlo simulation of the total radial distribution function for interlayer water in sodium and potassium montmorillonites. Clays and Clay Minerals, 47, 192–200.
Yamada, H., Nakazawa, H., Hashizume, H., Shimomura, S. and Watanabe, T. (1994) Hydration behavior of Na-smectite crystals synthesized at high-pressure and high-temperature. Clays and Clay Minerals, 42, 77–80.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wilson, J., Cuadros, J. & Cressey, G. An In situ Time-Resolved XRD-PSD Investigation into Na-Montmorillonite Interlayer and Particle Rearrangement during Dehydration. Clays Clay Miner. 52, 180–191 (2004). https://doi.org/10.1346/CCMN.2004.0520204
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.2004.0520204